U.S. patent application number 11/607015 was filed with the patent office on 2010-02-11 for regioregular polymerization of alpha-olefins to produce polyethylene with a predominance of methyl substituents.
This patent application is currently assigned to Cornell Research Foundation, Inc.. Invention is credited to Anna Cherian, Geoffrey W. Coates, Jeffrey M. Rose.
Application Number | 20100036077 11/607015 |
Document ID | / |
Family ID | 38163411 |
Filed Date | 2010-02-11 |
United States Patent
Application |
20100036077 |
Kind Code |
A1 |
Coates; Geoffrey W. ; et
al. |
February 11, 2010 |
Regioregular polymerization of alpha-olefins to produce
polyethylene with a predominance of methyl substituents
Abstract
Regioregular polymers of C.sub.4-C.sub.20 alpha-olefins of
M.sub.n greater than 1000 g/mol, are obtained.
Inventors: |
Coates; Geoffrey W.;
(Ithaca, NY) ; Cherian; Anna; (Ithaca, NY)
; Rose; Jeffrey M.; (Ithaca, NY) |
Correspondence
Address: |
CHOATE, HALL & STEWART LLP
TWO INTERNATIONAL PLACE
BOSTON
MA
02110
US
|
Assignee: |
Cornell Research Foundation,
Inc.
Ithaca
NY
|
Family ID: |
38163411 |
Appl. No.: |
11/607015 |
Filed: |
December 1, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60749029 |
Dec 12, 2005 |
|
|
|
Current U.S.
Class: |
526/348.3 ;
526/348.2 |
Current CPC
Class: |
C08F 297/08
20130101 |
Class at
Publication: |
526/348.3 ;
526/348.2 |
International
Class: |
C08F 10/14 20060101
C08F010/14 |
Goverment Interests
[0002] This invention was made at least in part with U.S.
Government support under U.S. Army Research Laboratory and the U.S.
Army Research Office under grant number DAAD 19-02-1-0275 MAP MURI
and using facilities supported through the NSF MRSEC program
(DMR-0079992). The government has certain rights in the invention.
Claims
1-7. (canceled)
8. A copolymer comprising units (A) and units selected from the
group consisting of (B), (C), and a combination of units (B) and
(C), where: ##STR00007## wherein: x ranges from 2 to 17 n ranges
from 1 to x+, M.sub.n ranges from 1,500 g/mol to 1,500,000 g/mol,
and there are more units (A) than units (B) and more units (A) than
units (C).
9. The polymer of claim 8 where there are no units (C).
10. The polymer of claim 8 where there are no units (B).
11. The polymer of claim 8 containing from up to 10% units (B), up
to 25% units (C), and at least 65% units (A).
12. (canceled)
13. The polymer of claim 11 containing at least 70% units (A).
14. The polymer of claim 8 where x is 2, 3, 4 or 5.
15. The polymer of claim 8 where x is 3.
16. A block copolymer wherein at least one block in the block
copolymer is a polymer as described in claim 8.
17-26. (canceled)
27. The polymer of claim 9 where x is 2.
28. The polymer of claim 10 where x is 2.
29-31. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 60/749,029, filed Dec. 12, 2005, the whole
of which is incorporated herein by reference.
TECHNICAL FIELD
[0003] This invention is directed to regioregular polymerization of
alpha olefin to produce substituted polyethylene.
BACKGROUND OF THE INVENTION
[0004] The coordination-insertion polymerization of .alpha.-olefins
using late transition metal catalysts typically occurs in a
regioirrregular fashion leading to polymer containing a variety of
enchainments, including but not limited to, 1,2
[--CH.sub.2CH((CH.sub.2).sub.x-3CH.sub.3)--], .omega.,2
[--CH(CH.sub.3)(CH.sub.2).sub.x-2--], and .omega.,1 [--CH.sub.2)--]
enchainments, where x is equal to the number of carbons in the
.alpha.-olefin. A random distribution of these and other
enchainments can result in a polymer with undesirable
properties.
[0005] In one case regioregular oligomerization of C.sub.3-C.sub.20
alpha olefins was carried out using a Ni.sup.0
aminobis(imino)phosphorane catalyst to obtain exclusively
.omega.,2-enchainment. However, the products had M.sub.n of only
about 1000. See Mohring, V. M., et al. Angew Chem. Int. Ed. 24,
1001-1003 (1985) and Fink, G., Polym. Mater. Sci. Eng. 64, 47-48
(1991).
SUMMARY OF THE INVENTION
[0006] It has been discovered herein that active transition metal
catalyst is available to provide regioregular polymerization of
C.sub.4-C.sub.20 alpha olefins resulting in product with M.sub.n
greater than 1,000 g/mol.
[0007] In one embodiment of the invention herein, denoted the first
embodiment, there is provided a method for preparing a polymer
comprising units (A)
##STR00001##
and none or one or both of units (B)
##STR00002##
and units (C)
##STR00003##
where x ranges from 1 to 17, n ranges from 1 to x+1, and M.sub.n
ranges from 1,500 g/mol to 1,500,000 g/mol, comprising the step of
polymerizing one or more C.sub.3+x alpha olefins in the presence of
active transition metal complex capable of alkene insertion with
the mole ratio of alpha-olefin to metal in the metal complex
ranging from 20:1 to 100,000:1 in a non-polar non-protic solvent at
a concentration of alpha olefin in the solvent ranging from 0.01 M
to 12 M using a reaction temperature ranging from -80.degree. C. to
+150.degree. C., to obtain polymer where there are more units (A)
than units (B) and more units (A) than units (C).
[0008] In another embodiment herein, denoted the second embodiment,
the invention is directed at a polymer comprising units (A) and
none or one or both of units (B) and (C) as recited in the first
embodiment herein where x ranges from 1 to 17, and M.sub.n ranges
from 1,500 g/mol to 1,500,000 g/mol, with more units (A) than units
(B) and more units (A) than units (C).
[0009] In still another embodiment herein, denoted the third
embodiment, the invention is directed to block copolymer with at
least one block which is polymer of the second embodiment and
method of making this.
[0010] The term "regioregular" as used herein means that the
monomers are enchained such that the molecular structure (atomic
connectivity) of the repeat units is the same in the resulting
polymer.
[0011] The term "regioirregular" as used herein means that monomers
are enchained such that the molecular structure (atomic
connectivity) of the repeat units is different in the resulting
polymer.
DETAILED DESCRIPTION
[0012] We turn now to the first embodiment herein.
[0013] In one case, the polymer obtained contains 65 to 100% units
(A), e.g. 65 to 96% or 98% units (A), 0 to 10% units (B) and 0 to
25% units (C).
[0014] In one case the polymer obtained has the structural
formula
##STR00004##
[0015] A preferred active transition metal complex capable of
alkene insertion has the formula
##STR00005##
where X can be a halogen atom, an alkoxide, a carbon-containing
group (such as a hydrocarbon), or a carboxylate where R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 can be the same or different, and are
each a hydrogen atom, a carbon containing group, e.g. a hydrocarbon
group, a halogen atom, a fluorocarbon group, a heterocyclic
compound residue, an oxygen-containing group, a nitrogen-containing
group, a boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a silicon-containing group, and two or
more of them may be bonded to each other to form a ring or rings,
and R.sup.5 and R.sup.6 are the same or different, and are each a
hydrogen atom, a halogen atom, a fluorocarbon group, a heterocyclic
compound residue, an oxygen-containing group, a nitrogen-containing
group, a boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a carbon-containing group (such as a
hydrocarbon), or a silicon-containing group, and they may be bonded
to each other to form a ring or rings, and R.sup.7 and R.sup.8 are
different and neither a hydrogen, and instead are each a halogen
atom, a fluorocarbon group, a heterocyclic compound residue, an
aromatic group, an oxygen-containing group, a nitrogen-containing
group, a boron-containing group, a sulfur-containing group, a
phosphorus-containing group, carbon-containing group (such as a
hydrocarbon), or a silicon-containing group, and they may be bonded
to each other to form a ring or rings. Each R.sup.1, each R.sup.2,
each R.sup.3, each R.sup.4, each R.sup.7 and each R.sup.8 can be
the same or different, that is both R's can be different in the
same molecule, both R.sup.2s can be different in the same molecule,
etc. These complexes are made as described in U.S. application Ser.
No. 11/508,333, the whole of which is incorporated herein by
reference.
[0016] A very preferred complex for alkene insertion for use herein
has the formula
##STR00006##
This complex is made as described in U.S. application Ser. No.
11/508,333 referred to above and incorporated herein by reference;
and in Cheman, A. E., et al., J. Am. Chem. Soc. 127, 13770-13771
(2005), the whole of which is incorporated herein by reference.
[0017] The complexes of formulas (II) and (III) are preferably used
together with cocatalyst which activates the complex to generate a
nickel alkyl cation which enchains the olefin(s) to produce
polymer, e.g. aluminum containing activator cocatalysts, e.g.,
MMAO-3A which has the approximate molecular formula
[(CH.sub.3).sub.0.7(isoC.sub.4H.sub.9).sub.0.3AlO].sub.n having the
approximate molecular weight 70.7 (7 wt % in heptane, Akzo Nobel),
PMAO-IP (polymethylaluminoxane--improved performance) (13 wt % in
toluene, Akzo Nobel) and diethylaluminum chloride. The activator
cocatalysts are used in cocatalyst metal complex nickel mole ratio,
e.g. an Al/Ni mole ratio ranging from 5:1 to 2000:1, e.g., 100:1 to
500:1.
[0018] The non-polar non-protic solvent can be, for example,
toluene, xylene, hexane or heptane and is preferably toluene.
[0019] The mole ratio of alpha olefin to metal in the metal complex
is preferably 500:1 to 10,000:1.
[0020] The concentration of alpha olefin in the non-polar
non-protic solvent preferably ranges from 0.1 M to 12 M.
[0021] The reaction temperature preferably ranges from -50.degree.
C. to +50.degree. C.
[0022] The time of reaction in the Working Examples was 2 to 24
hours.
[0023] It was found that the higher the olefin concentration and
the lower the reaction temperature, the greater the amount of units
(A) compared to the amount of units (B) and the greater the amount
of units (B) compared to units (C).
[0024] In one case, the first embodiment employs as monomer a
mixture of C.sub.3+x alpha olefin where x ranges from 1 to 17 and
one or more C.sub.2-C.sub.20 alkenes which are different from the
C.sub.3+x alpha olefin.
[0025] We turn now to the second embodiment herein.
[0026] Exemplary PDI ranges from 1.05 to 2.
[0027] In one case of the second embodiment, x is 1 and there are
no units (C).
[0028] In another case of the second embodiment, x is 2 and there
are no units (B).
[0029] The polymer of the second embodiment preferably contains at
least 30% units (A) and 0 to 10% units (B) and 0 to 25% units (C);
e.g., at least 50% units (A) and greater than 1% units (B), e.g.,
at least 65 or 70% units (A) and greater than 2% units (B) and
greater than 5% units (C). It is preferred for the polymer to
contain less than 10% units (C).
[0030] In one important case, x was 3 (i.e., the starting alpha
olefin was 1-hexene). In this case, M.sub.n ranging from about
9,000 g/mol to about 250,000 g/mol and PDI ranging from 1.08 to
1.21 were obtained.
[0031] In other cases, x was 1, 2, 4 or 5 and M.sub.n ranged from
30,000 g/mol to about 100,000 g/mol with PDI ranged from 1.06 to
1.26.
[0032] The polymers of the second embodiment have utility as
substitutes for poly(ethylene-co-propylenes) and have uses as
thermoplastic elastomers.
[0033] We turn now to the third embodiment. We turn to various
methods for preparing block copolymers of the third embodiment and
the products therefrom. The catalysts and cocatalysts employed are
the same as for the first embodiment.
[0034] In one case the reaction conditions, e.g. temperature,
monomer concentration, solvent polarity, of the first embodiment
are varied during reaction so that a block copolymer is obtained
comprising blocks each comprising units (A) and none or one or both
units (B) and (C) and there are more units (A) than units (B) and
more units (A) than units (C), with different proportions of (A),
(B) and (C) in each block; in this case (B) and/or (C) must be
present in at least one block and can be present in two or more
blocks. The product may be described as a multi-block
copolymer.
[0035] In another case, the monomers are a mixture of C.sub.3+x
alpha olefins where x ranges from 1 to 17 and one or more
C.sub.2-C.sub.20 alkenes which are different from the C.sub.3+x
alpha olefins and reaction conditions e.g. temperature, monomer
concentration, solvent polarity, of the first embodiment are varied
during the polymerization to obtain blocks of each comprising units
(A) and none or one or both of units (B) and none or one or both of
units (C), with different proportions of (A), (B) and (C) in each
block; in this case (B) and/or (C) must be present in at least one
block.
[0036] In still another case, the monomers for the first embodiment
are C.sub.3+x alpha olefins where x ranges from 1 to 17 and one or
more C.sub.2-C.sub.20 alkenes different from the C.sub.3+x alpha
olefin and/or mixtures of these added and/or polymerized at
different times during the reaction to obtain at least one block
comprising units (A) and none or one or both of units (B) and units
(C) with more units (A) than units (B) and more units (A) than
units (C). In this case, when the C.sub.2-C.sub.20 alkene is a
C.sub.4-C.sub.20 alpha-olefin, the at least two blocks comprising
units (A) and none or one or both of units (B) and (C) with more
units (A) than units (B) and more units (A) than units (C), with
different proportions of (A), (B) and (C) in each block; in this
case (B) and/or (C) must be present in at least one block.
[0037] M.sub.n, M.sub.w and polydispersities (PDI, M.sub.w/M.sub.n)
are determined by high temperature gel permeation chromatography
(GPC). Analyses were performed with a Waters Alliance GPCV 2000 GPC
equipped with a Waters DRI detector and viscometer. The column set
(four Waters HT 6E and one Waters HT2) was eluted with
1,2,4-trichlorobenzene containing 0.01 wt %
di-tert-butylhydroxytoluene (BHT) at 1.0 mL/min at 140.degree. C.
Data were calibrated using monomodal polyethylene standards (from
Polymer Standards Service).
[0038] Elements of the invention and Working Examples are found in
Rose, J. M., Cheman, A. E. and Coates, G. W., J. Am. Chem. Soc.
128, 4186-4187 (published on web on Mar. 11, 2006, hereinafter said
JACS article, and pages S1-S19 of Supporting Information therefore,
hereinafter said Supporting Information, the whole of both of which
are incorporated herein by reference.
[0039] The invention is illustrated by the following working
examples.
Working Example I
[0040] Polymerization of 1-hexene in the presence of catalyst of
structure III is set forth at pages S3, S4 and S5 of said
Supporting Information.
Working Example II
[0041] Polymerization of 1-hexene in the presence of catalyst of
structure III is set forth at page S5 of said Supporting
Information.
Working Example III
[0042] Polymerization of 1-heptene in the presence of catalyst of
structure III is set forth at page S5 of said Supporting
Information.
Working Example IV
[0043] Polymerization of 1-octene in the presence of catalyst of
structure III is set forth at S5 of said Supporting
Information.
Working Example V
[0044] Polymerization of 1-butene in the presence of catalyst of
structure III is set forth at pages S5 and S6 of said Supporting
Information.
Working Example VI
[0045] Conditions for and results for nine 1-hexene polymerizations
are given in Table 1 of said JACS article.
Working Example VII
[0046] Conditions for and results for polymerization five different
alpha-olefins are given in Table 2 of said JACS article.
Working Example VIII
[0047] In a 1-liter round bottom flask, under nitrogen, was added
1-pentene (100.0 mL), toluene (330 mL) and MMAO-3A (25 mmol). The
mixture was cooled to -20.degree. C. and after 10 minutes of
equilibration, complex III (100 .mu.mol) as a solution in
CH.sub.2Cl.sub.2 (10 mL) was injected. After 2 hr an aliquot was
taken from the reaction mixture and quenched with methanol and the
flask was transferred to a 0.degree. C. bath. After 5.1 h, a second
aliquot was taken and quenched and the flask was transferred back
to the -20.degree. C. bath. The polymerization was quenched with
MeOH 12 hr later after which the reaction mixture was poured into
copious acidic MeOH. The polymer was filtered after stirring in
acidic MeOH for approximately 12 h then dried in vacuo at
60.degree. C. to give a mass of 16.61 g. The triblock has block
M.sub.n values of 62,400 g/mol, 40,400 g/mol, and 31,600 g/mol for
blocks A, B, and C, respectively. For the overall polymer
M.sub.n=134,400 g/mol and PDI -1.15. For block A, the mole fraction
ratio of each unit type (A:B:C) was 0.69:0.22:0.09; for B, the mole
fraction ratio for each unit type (A:B:C) was 0.84:0.10:0.06. It
had T.sub.g=64.7.degree. C. and T.sub.m=100.1.degree. C.
Working Example IX
[0048] To a 12 oz. glass pressure reactor was added 1-pentene (11
mL), toluene (85 mL), and MMAO-7 (4 mmol). The reactor was cooled
to -20.degree. C. after which ethylene (10 psi) was added. Complex
III (20 .mu.mol) was injected as a solution in CH.sub.2Cl.sub.2 (2
mL). The polymerization was quenched with MeOH 25 min later, after
which the reaction mixture was poured into copious acidic MeOH. The
polymer was filtered after stirring in acidic MeOH for
approximately 12 hrs then dried in vacuo at 60.degree. C. to give a
mass of 1.11 g. The copolymer had M.sub.n--127,100 g/mol and
PDI=1.08. It contained 73 mol % (--CH.sub.2--) units, 23 mol %
(--CH(CH.sub.3)--) units, and 3 mol % (--CH(R)--) units where
R=C.sub.nH.sub.2N+1 and n>1. It had T.sub.g=-52.8.degree. C. and
T.sub.m=27.4.degree. C.
Working Example X
[0049] To a 12 oz. glass pressure reactor was added 1-pentene (63.5
mL), toluene (206 mL), and MMAO-3A (32.6 mmol). The reactor was
cooled to -78.degree. C. after which 1-butene (33.25 g) was
condensed in. The reactor was then transferred to an ice bath and
allowed to equilibrate for 20 min after which an overpressure of
propylene (20 psi) was added. After equilibration for an additional
10 min, complex III (130 .mu.mol) was injected as a solution in
CH.sub.2Cl.sub.2 (8 mL). The polymerization was quenched with MeOH
3.1 hours later after which the reaction mixture was poured into
copious acidic MeOH. The polymer was filtered after stirring in
acidic MeOH for approximately 12 h, then dried in vacuo at
60.degree. C. to give a mass of 12.5 g. The terpolymer had
M.sub.n=91,400 g/mol and PDI=1.23. It contained 78 mol %
(--CH.sub.2--) units, 20 mol % (--CH(CH.sub.3)--) units, and 2 mol
% (--CH(R)--) units where R=C.sub.nH.sub.2n+1 and n>1.
Working Example XI
[0050] To a 12 oz. glass pressure reactor was added toluene (100
mL) and MMAO-7 (6 mmol). The reactor was cooled to -20.degree. C.
after which ethylene (10 psi) was added. Complex III (30 .mu.mol)
was injected as a solution in 5 mL CH.sub.2Cl.sub.2 (8 mL). After
10 minutes, the reactor was vented and ethylene was removed in
vacuo. 1-Pentene (30 mL) was then added. After 5 hr, 1-pentene was
removed in vacuo, and ethylene (10 psi) was added. The
polymerization was quenched with MeOH 10 minutes later, after which
the reaction mixture was poured into copious acidic MeOH. The
polymer was filtered after stirring in acidic MeOH for
approximately 12 hours then dried in vacuo at 60.degree. C. to give
a mass of 1.11 g. The triblock had block M.sub.n values of 47,600
g/mol, 33,800 g/mol, and 5,900 g/mol for blocks A, B, and C,
respectively. For the overall polymer, M.sub.n=87,300 g/mol and PDI
-1.11. For block B, the mole fraction ratio of each unit type
(A:B:C) was 0.97:0.03:0.0. Blocks (A) and (C) are linear
polyethylene with less than one CH.sub.3 group per 100 CH.sub.2
groups. The triblock copolymer had T.sub.g=63.3.degree. C. and
T.sub.m=122.5.degree. C.
Working Example XII
[0051] An equimolar mixture of 1-pentene and 1-hexene in toluene is
polymerized at minus 20.degree. C. using complex III activated with
methyaluminoxane to form block A. The temperature of the
polymerization is then raised to 0.degree. C. to form block B which
differs in the proportions of units A, B, and C relative to block
A. Lastly, the polymerization temperature is lowered back to
-20.degree. C. to form block C which differs in the proportions of
units A, B, and C relative to blocks A and B.
Working Example XII
[0052] A solution of 1-pentene in toluene is polymerized using
complex III activated with methylaluminoxane to form block A. To
the unreacted 1-pentene is added 1-hexene, and this mixture is then
copolymerized to form block B which differs in the proportions of
units A, B, and C relative to block A. Lastly, block C is formed
when all of the 1-hexene is consumed in the polymerization. Block C
differs in the proportions of units A, B, and C relative to blocks
A and B.
VARIATIONS
[0053] The foregoing description of the invention has been
presented describing certain operable and preferred embodiments. It
is not intended that the invention should be so limited since
variations and modifications thereof will be obvious to those
skilled in the art, all of which are within the spirit and scope of
the invention.
* * * * *